Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3- Anion Acting as a Monodentate Ligand: See abstract

Article abstract of DOI:10.1002/zaac.200300158

The two novel thioantimonate(V) compounds [Mn(C₆H ₁₈N₄)(C₆H₁₉N₄)]SbS ₄ (I) and [Mn(C₆H₁₄N₂) ₃]₂-[Mn(C₆H₁₄N₂) ₂(SbS₄)₂]·6H₂O (II) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2-aminoethyl)amine (tren) at 140°C or chxn (trans-1,2-diaminocyclohexane, aqueous solution 50%) at 130°C. Compound I crystallises in the triclinic space group P1, a = 9.578(2), b = 11.541(2), c = 12.297(2) A, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4) A³, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1) A, β = 117.237(5)°, V = 7931.7(8) A³, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS ₄]^3- anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄] ^3- units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.

Full text of DOI:10.1002/zaac.200300158

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V)
3؊
Compounds with the [SbS ] Anion Acting as a Monodentate Ligand:
4
[
[
Mn(C H N )(C H N )]SbS and
6
18 4
6
19 4
4
Mn(C H N ) ] [Mn(C H N ) (SbS ) ]·6H O
6
14 2 3 2
6
14 2 2
4 2
2
Michael Schaefer, Lars Engelke, and Wolfgang Bensch*
Kiel, Institut für Anorganische Chemie der Christian-Albrechts Universität
th
Received May 9 , 2003.
Abstract. The two novel thioantimonate(V) compounds
protonated tren acting as a monodentate ligand and a monodentate
3
Ϫ
[
[
Mn(C
Mn(C
6
H
H
18
N
N
4
)(C
6
H
19
N
4
)]SbS
4
(I)
and
[Mn(C
6
H
14
N
2
)
3
]
2
-
[SbS
4
]
anion yielding a distorted octahedral environment. In II
2
ϩ
6
14
2
)
2
(SbS
4
)
2
]·6H O (II) were synthesized under solvo-
2
one unique Mn ion is in an octahedral environment of three
bidentate chxn molecules and the second independent Mn ion is
2
ϩ
thermal conditions by reacting elemental Mn, Sb and S in the stoi-
chiometric ratio in 5 ml tris(2-aminoethyl)amine (tren) at 140 °C
3
Ϫ
4
coordinated by two chxn ligands and two monodentate [SbS ]
or chxn (trans-1,2-diaminocyclohexane, aqueous solution 50 %) at
units leading to a distorted octahedral surrounding. The com-
pounds were investigated and characterized with thermal and spec-
troscopic methods.
¯
1
30 °C. Compound I crystallises in the triclinic space group P1,
˚
a ϭ 9.578(2), b ϭ 11.541(2), c ϭ 12.297(2) A, α ϭ 62.55(1), β ϭ
˚
3
85.75(1), γ ϭ 89.44(1)°, V ϭ 1202.6(4) A , Z ϭ 2, and II in the
monoclinic space group C2/c, a ϭ 32.611(2), b ϭ 13.680(1), c ϭ
˚
˚
3
1
9.997(1) A, β ϭ 117.237(5)°, V ϭ 7931.7(8) A , Z ϭ 4. In I the
Keywords: Thioantimonate; Solvothermal synthesis; Thermal sta-
bility; Raman spectroscopy
2ϩ
Mn cation is surrounded by one tetradentate tren molecule, one
Solvothermale Synthese und Kristallstrukturen zweier Thioantimonat(V)-Verbindungen
3
؊
mit dem einzähnig wirkenden [SbS ] -Anion: [Mn(C H N )(C H N )]SbS und
4
6
18
4
6
19
4
4
[
Mn(C H N ) ] [Mn(C H N ) (SbS ) ]·6H O
6
14 2 3 2
6
14 2 2
4 2
2
117,237(5)°, V ϭ 7931,7(8) A , Z ϭ 4. In I ist das Mn2ϩ-Kation
von einem vierzähnigen tren-Liganden, einem einfach protonier-
ten, einzähnigen tren-Liganden sowie einem einzähnig wirkenden
˚
3
Inhaltsübersicht.
Die
beiden
)]SbS
]·6H O (II) werden unter solvothermalen
neuen
Thioantimonate(V)
[Mn(C H N ) ] -
6 14 2 3 2
[
[
Mn(C
Mn(C
6
H
H
18
N
N
4
)(C
6
H
19
N
4
4
(I)
und
6
14
2
)
2
(SbS
4
)
2
2
3
Ϫ
Bedingungen bei der Reaktion von Mangan, Antimon und Schwe-
fel im stöchiometrischen Verhältnis in 5 ml Tris(2-Aminoethyl)-
amin (tren) bei 140 °C oder chxn (trans-1,2-Diaminocyclohexan,
[SbS ] -Anion verzerrt oktaedrisch umgeben. In II befindet sich
ein unabhängiges Mn -Ion in einer oktaedrischen Umgebung aus
drei zweizähnigen chxn-Liganden, das zweite unabhängige Mn
4
2
ϩ
2
ϩ
-
5
0 %-ige Lösung) bei 130 °C gebildet. Verbindung I kristallisiert in
Ion ist verzerrt oktaedrisch von zwei chxn-Liganden sowie zwei
einzähnigen [SbS ] -Einheiten koordiniert. Die Verbindungen
4
wurden mit thermischen und spektroskopischen Methoden unter-
sucht und charakterisiert.
¯
˚
˚
3Ϫ
der triklinen Raumgruppe P1, a ϭ 9,578(2) A, b ϭ 11,541(2) A,
c ϭ 12,297(2) A, α ϭ 62,55(1)°, β ϭ 85,75(1)°, γ ϭ 89,44(1)°, V ϭ
1
˚
˚
3
202,6(4) A , Z ϭ 2, und II in der monoklinen Raumgruppe C2/c,
˚
˚
˚
a ϭ 32,611(2) A, b ϭ 13,680(1) A, c ϭ 19,997(1) A, β ϭ
Introduction
During the systematic exploration of the systems with
TM ϭ Ni and Co applying the amines diethylenetriamine
During the last few years we have investigated several TM-
Sb-S-amine systems (TM ϭ transition metal) with the aim
to synthesise new thioantimonates(III) that contain TM
ions as part of the thioantimonate networks. Thioantimon-
ates(III) with such TM ions should exhibit new structural
architectures and interesting physico-chemical properties.
(dien) and tris(2-aminoethyl)amine (tren) we synthesized
and characterized several new thioantimonates where
nϩ
nϩ
TM ions were successfully integrated into the Sb S net-
x
y
work, e.g. [Ni(dien) ] Sb S [1], [Co(tren)] Sb S , [Co-
2
2
4
8
2
4 8
nϩ
(
tren)] Sb S [2], [Co(tren)]Sb S , and [Ni(tren)]Sb S [3]. A
2 2 5 2 4 2 4
highly interesting result of our experiments is that in only
V
rare cases Sb is oxidized to Sb under the very basic con-
ditions of the syntheses. In the overwhelming number of
compounds antimony is present as Sb and there are com-
III
*
Prof. Dr. W. Bensch
Institut für Anorganische Chemie der Universität Kiel
Olshausenstr. 40
D-24098 Kiel
Fax: ϩ49 (0)431/880 Ϫ1520
e-Mail: wbensch@ac.uni-kiel.de
paratively few examples for thioantimonates(V) [4Ϫ12]. In
V
most Sb S compounds the cations and anions are well
3Ϫ
separated and interconnection of [SbS4]
anions was only
found in few samples [6, 8Ϫ11]. During our systematic
1912
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
DOI: 10.1002/zaac.200300158
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds
4
Fig. 1 Crystal structure of [Mn(tren)(trenH)]SbS with labelling.
The H atoms and the disordered atoms are omitted.
]2
ϩ
cation in
Fig.
Mn(chxn)
and the disordered atoms are omitted.
2
Structure of the [Mn(1)(chxn)
3
[
3
]
2
[Mn(chxn) (SbS ]·6H O with labelling. The H atoms
2
4
)
2
2
˚
Table 1 Selected structure parameters (A / °) for [Mn(tren)
4 3 2 2 4 2 2
(trenH)]SbS (I) and [Mn(chxn) ] [Mn(chxn) (SbS ) ]·(6H O (II).
Estimated standard deviations are given in parenthesis.
I
Sb-S(1)
Sb-S(3)
Mn-N(1)
Mn-N(3)
Mn-N(6)
2.3604 (9)
2.319 (1)
2.341 (3)
2.238 (3)
2.216 (2)
Sb-S(2)
Sb-S(4)
Mn-N(2)
Mn-N(4)
Mn-S(1)
2.326 (1)
2.3148 (9)
2.298 (3)
2.316 (3)
2.653 (1)
S(1)-Sb-S(2)
S(1)-Sb-S(4)
S(2)-Sb-S(4)
Sb-S(1)-Mn
N(1)-Mn-N(3)
N(1)-Mn-N(6)
105.06 (4)
109.37 (3)
110.98 (4)
111.87 (3)
77.1 (1)
S(1)-Sb-S(3)
S(2)-Sb-S(3)
S(3)-Sb-S(4)
N(1)-Mn-N(2)
N(1)-Mn-N(4)
N(1)-Mn-S(1)
108.71 (4)
111.28 (4)
111.22 (4)
75.3 (1)
75.4 (1)
102.26 (8)
160.0 (1)
II
Sb-S(1)
Sb-S(3)
Mn(1)-N(1)
Mn(1)-N(3)
Mn(1)-N(5)
Mn(2)-N(7)
Mn(2)-S(1)
2.335 (1)
2.329 (1)
2.283 (3)
2.276 (3)
2.258 (3)
2.235 (4)
2.700 (1)
Sb-S(2)
Sb-S(4)
Mn(1)-N(2)
Mn(1)-N(4)
Mn(1)-N(6)
Mn(2)-N(8)
2.348 (1)
2.323 (1)
2.253 (1)
2.316 (3)
2.280 (3)
2.255 (4)
Structure of the [Mn(2)(chxn) (SbS ) ]4Ϫ anion in
3
2 4 2
Fig.
3 2 2 4 2 2
Mn(chxn) ] [Mn(chxn) (SbS ) ]·6H O with labelling. The H atoms
[
and the disordered atoms are omitted.
S(1)-Sb-S(2)
S(1)-Sb-S(4)
S(2)-Sb-S(4)
N(1)-Mn(1)-N(2)
N(1)-Mn(1)-N(4)
N(1)-Mn(1)-N(6)
N(3)-Mn(1)-N(4)
N(7)-Mn(2)-S(1)
109.56 (4)
108.90 (4)
110.64 (4)
77.3 (1)
91.8 (1)
92.9 (1)
S(1)-Sb-S(3)
S(2)-Sb-S(3)
S(3)-Sb-S(4)
N(1)-Mn(1)-N(3)
N(1)-Mn(1)-N(5)
N(7)-Mn(2)-N(8)
N(5)-Mn(1)-N(6)
N(8)-Mn(2)-S(1)
109.40 (4)
108.51 (4)
109.81 (6)
96.6 (1)
169.3 (1)
77.5 (2)
Results
In the two new compounds [Mn(tren)(trenH)]SbS (I) and
4
2ϩ
[Mn(chxn) ] [Mn(chxn) (SbS ) ]·6H O (II) the Mn ions
3 2 2 4 2 2
have an octahedral-like environment. In compound I all
atoms are on general positions. The Mn2 ion is sur-
rounded by five N atoms from two different tren ligands
76.0 (1)
85.5 (1)
77.1 (1)
89.8 (1)
ϩ
(Fig. 1). One tren molecule acts as a tetradentate ligand and
the other shows a monodentate behavior. The coordination
2ϩ
sphere around Mn is completed by the S(1) atom of the
[SbS4]3 anion (Fig. 1). The Mn-S bond length of
Ϫ
investigation of the Mn-Sb-S-tren and Mn-Sb-S-chxn sys-
tems we obtained two new thioantimonates(V) [Mn(tren)-
˚
2.653(1) A is in the normal range. The Mn-N distances vary
˚
(
trenH)]SbS4 and [Mn(chxn) ] [Mn(chxn) (SbS ) ]·6H O
between 2.216(2) and 2.341(3) A with N-Mn-N angles rang-
3 2
2
4 2
2
3
Ϫ
with the [SbS4] anion acting as a monodentate ligand.
Here we report the syntheses, crystal structures, the thermal
stability and the Raman spectra of the new compounds.
ing from 75.3(1) to 160.0(1)° (Table 1). Angles and dis-
tances are comparable with those reported in the literature
˚
[13Ϫ18] and in II. The Mn atom is 0.3247 A above the
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918
zaac.wiley-vch.de
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1913

M. Schaefer, L. Engelke, W. Bensch
˚
Table 2 Selected H···S distances (A) and angles (°) for [Mn(tren)-
trenH)]SbS (I) and [Mn(chxn) [Mn(chxn) (SbS ]·6H O (II).
(
4
3
]
2
2
4
)
2
2
D-H
A
d(D-H) d(H..A) <DHA d(D..A) Symmetry code
I
N2-H1N2 S3 0.900
N2-H2N2 S3 0.900
N3-H1N3 S3 0.900
N3-H2N3 S2 0.900
N4-H1N4 S4 0.900
N4-H2N4 S4 0.900
N6-H1N6 S3 0.900
N6-H2N6 S2 0.900
N7-H1N7 S2 0.796
N7-H2N7 S1 0.841
N7-H3N7 S4 1.018
2.810
2.488
2.511
2.613
2.756
2.795
2.739
2.681
2.651
2.502
2.393
159.45 3.666
156.95 3.335
171.89 3.404
148.33 3.412
153.24 3.582
155.34 3.632
168.39 3.625
158.02 3.532
160.12 3.411
143.05 3.214
148.37 3.303
Ϫxϩ1, Ϫyϩ1, Ϫzϩ1
xϪ1, y, z
Ϫxϩ1, Ϫyϩ1, Ϫzϩ1
xϪ1, y, z
Ϫxϩ1, Ϫyϩ1, Ϫzϩ2
Ϫxϩ1, Ϫyϩ1, Ϫzϩ1
Ϫxϩ1, Ϫyϩ1, Ϫzϩ2
Ϫxϩ1, Ϫyϩ1, Ϫzϩ2
II
N2-H2N2 S4 0.900
N3-H2N3 S2 0.900
N5-H2N5 S3 0.900
N6-H1N6 S1 0.900
N6-H2N6 S2 0.900
N1-H1N1 O2 0.900
N3-H1N3 O2 0.900
N4-H1N4 O1 0.900
N5-H1N5 O1 0.900
2.660
2.929
2.593
2.712
2.785
2.263
2.475
2.219
2.361
163.70 3.533
167.94 3.813
152.62 3.417
156.41 3.555
143.38 3.548
163.37 3.136
149.01 3.279
167.01 3.102
155.09 3.200
x, Ϫyϩ1, zϪ0.5
x, Ϫyϩ1, zϪ0.5
plane formed by N(2), N(3), N(4) and S(1). We note that
tren complexes of transition metal ions are well known but
only few manganese compounds with tren (and its deriva-
tives) were synthesized until now [13, 14]. In the [SbS4]3
Ϫ
anion the Sb-S bond lengths scatter from 2.3148(9) to
Fig. 4 (top) Arrangement of [Mn(tren)(trenH)]SbS
tallographic a-axis; (bottom) Arrangement of [Mn(tren)-
trenH)]SbS along the crystallographic b-axis.
4
along the crys-
˚
2.3604(9) A and the S-Sb-S angles range from 105.06(4) to
1
11.28(4)° (Table 1). These values are typical for slightly
(
4
3
Ϫ
distorted tetrahedral [SbS4]
anions [4, 5, 7, 12]. The
monodentate amine is protonated at the N(7) atom and all
H atoms bound to this N atom were located in the differ-
ence Fourier map. The C-C and C-N bond lengths are as
expected for single bonds.
symmetry operation and the resulting S-Mn-S angle is 180°.
The Sb-S bond lengths are in a narrow range between
˚
2.323(1) and 2.348(1) A and S-Sb-S angles range from
In II all atoms except Mn(2) are on general positions.
108.51(4) to 110.64(4)°. These geometrical parameters indi-
2
ϩ
The crystallographically independent Mn(1) ion is coor-
dinated by six N atoms of three bidentate amine molecules
forming the cationic species of the compound
cate a less strong distortion of the SbS tetrahedron than
4
in I. The Mn(2)-N distances are between 2.235(4) and
˚
2.255(4) A. A moderate distortion of the Mn(2)N S octa-
4
2
2
ϩ
[
2
Mn(chxn)3] (Fig. 2). The Mn(1)-N bonds scatter from
hedron is indicated by the N-Mn-N/S-Mn-N angles (Table
1).
˚
.253(3) to 2.316(3) A and the resulting octahedron is dis-
torted with N-Mn-N angles ranging from 76.0(1) and
69.3(1)° (Table 1). Distances and angles agree well with
In both compounds the S atoms are involved in hydrogen
bonds to H atoms bound to N atoms (Table 2). Although
hydrogen bonding interactions are generally weak, they
contribute to the stability of the structures and are impor-
tant for the determination of the crystal packing.
The molecules in I are stacked in a rod-like manner pa-
rallel to the crystallographic axes and two different views
are shown in Figure 4. Defining the non-bonded end of the
1
data reported in the literature [13Ϫ18] and with the struc-
tural parameters in I.
The second cation Mn(2) is located on a centre of in-
version and is surrounded by two chxn ligands and two
2
ϩ
SbS tetrahedra which are in trans position to each other
4
(
Fig. 3). Hence, the environment can be derived simply by
2
ϩ
replacing one chxn ligand of the [Mn(1)(chxn) ] cation
by two [SbS4]
compound [Mn(chxn) (SbS ) ] . The Mn(2)-S(1) bond of
tren molecule as the tail and the MnN S octahedron as the
3
5
3
Ϫ
anions yielding the anionic part of the
head of the molecules the neighboured molecules show a
head-to-tail orientation within the (100) plane (Fig. 4, top).
Looking along the b-axis the molecules are arranged in a
layer-like fashion with a separation between successive
4
Ϫ
2
4 2
˚
2
.700(1) A is slightly longer than the Mn-S distance in I
which may be caused by the sterical demand of the chxn
˚
ligands. The two SbS tetrahedra are generated by the Ϫ1
layers of about 3.9 A (Fig. 4, bottom).
4
1914
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds
Fig.
3 2 2 4 2 2
6 Arrangement of [Mn(chxn) ] [Mn(chxn) (SbS ) ]·6H O
along the crystallographic a-axis. The H atoms and the disordered
atoms are omitted.
4 2
)
]4Ϫ anions (top)
Fig. 5 Arrangement of the [Mn(2)(chxn)
2
(SbS
cations (bottom) in the crystal structure
[Mn(chxn) (SbS ]·6H O. The H atoms, O atoms
and the disordered atoms are omitted.
2ϩ
and of the [Mn(chxn)
of [Mn(chxn)
3
]
3
]
2
2
4
)
2
2
Fig.
Mn(chxn)
other compounds containing [SbS
7
Raman spectra of [Mn(tren)(trenH)]SbS
4
(I) and
[
3
]
2
[Mn(chxn) (SbS ]·6H O (II) in comparison with
2
4
)
2
2
Ϫ
]3 anions.
4
In compound II the anions are located on the corners of
the unit cell, in the middle of the c-axis, in the centre of the
cell and on the ab plane (Fig. 5a). The cations are located
in interstices formed by the anions (Fig. 5b). Perpendicular
to [010] the stacking sequence of each species is ABA (Fig.
The DTA-TG curves of the thermal decomposition reac-
tions of I and II are depicted in Figure 8. Both compounds
decompose in a complex step-wise fashion. For I a mass
loss starts at about 125 °C and at least three steps can be
identified in the DTG curve until 350 °C (Fig. 8, top). Each
reaction is accompanied by an endothermic signal in the
6). Due to the sterical demand of the amines the packing
of the cations and anions is very open and holes are created
which host the water molecules (Fig. 6). The water mol-
ecules have several short contacts to N and S atoms indica-
tive for N-H···O and O-H···S hydrogen bonds (see Table 2).
Figure 7 shows the Raman spectra of the title compounds
together with that of Na SbS · 9 H O [12] and [Ni(di-
DTA curve (Tp ϭ 193.6 °C, Tp ϭ 240.6 °C, and Tp
ϭ
298.4 °C). The total relative mass loss amounts to -∆m ϭ
51.2 %. Interestingly, elemental Sb and MnS were identified
in the X-ray powder diffraction pattern indicating that a
complex redox reaction occurs during the thermal degra-
dation. For a better understanding of the decomposition
mass spectra were recorded simultaneously during the reac-
3
4
2
en) ] (SbS ) [7] for comparison. In the spectrum of I two
2
3
4 2
Ϫ1
intense modes are located at 390 and 372 cm with an-
other not fully resolved signal at 363 cm whereas for II
the absorptions are observed at 375 and 356 cm . Accord-
Ϫ1
Ϫ1
tion. In the mass spectrum the signal of H S (m/z ϭ 34)
2
ing to the data reported in the literature [19, 20] the energy
and fragments of the ligand (m/z ϭ 99) were detected. As-
of the resonances is typical for Sb-S vibrations. In Na SbS4
suming that both tren ligands and two H S molecules are
3
2
·
9 H O and [Ni(dien) ] (SbS ) the anions are isolated
emitted the expected mass change amounts to 54.6 %. The
difference to the experimental value may be explained by
residues of C and N (total: 6.5 %) in the grey decompo-
sition product. In a second experiment the reaction was
2
2 3
4 2
2
ϩ
whereas in I and II one S atom has a bond to Mn . There-
fore, the differences observed in the spectra may be due to
the different bonding situations in the distinct compounds.
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918
zaac.wiley-vch.de
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1915

M. Schaefer, L. Engelke, W. Bensch
Table 3 Crystal data and results of the structure refinement for
4
[Mn(tren)(trenH)]SbS (I) and
[
Mn(chxn) [Mn(chxn)
3
]
2
2
4 2 2
(SbS ) ]·6H O (II).
Compound
I
II
Crystal system
triclinic
9.578 (2)
monoclinic
32.611 (2)
13.680 (1)
19.997 (1)
90
117.237 (5)
90
7931.7 (8)
C2/c
4
1.409
yellow
0.2ϫ0.2ϫ0.1
1686.40
1.40
˚
a / A
˚
b / A
11.541 (2)
12.297 (2)
62.55 (1)
85.75 (1)
89.44 (1)
1202.6 (4)
P-1
˚
c / A
α / °
β / °
γ / °
˚
3
V / A
Space group
Z
Calc. density / g cm
Crystal color
Crystal size / mm
2
Ϫ3
1.653
yellow
5ϫ1ϫ1
598.43
2.01
Ϫ1
Molecular weight / g mol
Ϫ1
µ / mm
F(000)
Scan range
Index range
610
3492
4° Յ 2θ Յ 54°
Ϫ0 Յ h Յ 10
Ϫ14 Յ k Յ 14
Ϫ15 Յ l Յ 15
5477
5° Յ 2θ Յ 56°
Ϫ42 Յ h Յ 41
Ϫ18 Յ k Յ 18
Ϫ25 Յ l Յ 25
36741
Reflections collected
Independent reflections
4913
3703
9232
6102
Refl. with F
o
>4σ(F
o
)
R
int
0.021
0.0514
a)
weight
Temperature/K
yϭ0.0287/zϭ0.1871 yϭ0.0693/zϭ6.477
293
293
Absorption correction
Min./max. transmission
Number of parameters
none
Ϫ
270
0.0257
0.0608
1.018
0.47 / Ϫ0.36
numerical
0.7784 / 0.8574
408
0.0766
0.1271
1.015
1.07 / Ϫ0.63
R
1
for F
wR for all reflections
GoF
Res. elec. density in e/A
o
>4σ(F
o
)
2
˚
3
a)
2
o o c
w ϭ 1/[σ (F ) ϩ (y·P) ϩ z·P]; P ϭ (Max (F
2,0) ϩ 2·F 2) / 3
2
2
5
different steps can be identified with a total weight loss
of about 59.5 %. This experimental value is in good agree-
ment with the expected weight loss assuming the emission
of the organic ligands and the water molecules (Ϫ∆m ϭ
6
0.58 %). The different thermal reactions are accompanied
Fig. 8 (top) DTA, TG and DTG (dotted line) curves of [Mn(tren)-
by endothermic signals in the DTA curve. A distinct assign-
ment of the different steps is not an easy task but roughly
the first weight change (T ϭ 139 °C in the DTA curve) of
about 18 % is in accordance with the loss of two amine
Ϫ1
(
(
trenH)]SbS
bottom) DTA, TG and DTG (dotted line) curves of
[Mn(chxn) (SbS ]·6H O (atmosphere: N ; heating
4
(atmosphere:
N
2
;
heating rate: 4 K min );
[Mn(chxn)
3
]
2
2
4
)
2
2
2
p
Ϫ1
rate: 4 K min ).
molecules and one water molecule (Ϫ∆m ϭ 19.9 %). The
next pronounced step (T ϭ 197.5 °C) is accompanied by a
p
stopped after the first decomposition step. The orange col-
ored crystalline residue contained 19.4 % C, 4.6 % H,
weight loss of 14 % which agrees with the emission of two
additional amine molecules (Ϫ∆m ϭ 13.54 %). During the
13.9 % N, 17.7 % S and the Mn:Sb:S ratio was determined
last thermal reaction (Ϫ∆m ϭ 27.5 %, T ϭ 253.5 °C) the
p
by EDX to 1:2:6. In the X-ray powder pattern reflections
of crystalline MnS and intense reflections of an unknown
compound are seen. The reflections could be indexed on
the basis of triclinic symmetry with the lattice parameters
remaining amine molecules are emitted (expected Ϫ∆m ϭ
27.1 %). In two further experiments the decomposition was
stopped at 170 °C and at 220 °C. The EDX analyses of the
intermediates showed a Mn:Sb:S ratio of 3:2:7.2 indicating
that S was also removed during the thermal reactions. This
assumption is supported by the chemical analysis. After the
first reaction the material is still crystalline and the X-ray
powder pattern is typical for a layered compound and is
˚
˚
˚
a ϭ 11.015 A, b ϭ 13.839 A, c ϭ 16.027 A, α ϭ 102.60°,
˚
3
β ϭ 95.24° and γ ϭ 104.93°, V ϭ 2275.3 A . According to
the analyses the first thermal decomposition reaction may
be formulated as 2 [Mn(C H N )]SbS Ǟ MnS ϩ
1
2
37
8
4
˚
[
Mn(C H N )]Sb S ϩ H S ϩ 2 C H N .
dominated by a very intense reflection at d ϭ 13.1 A. After
1
2
36
8
2
6
2
6
18
4
The thermal decomposition of II seems to be more com-
plex as can be seen from the DTG curve (Fig. 8). At least
the second thermal event the X-ray powder pattern indi-
cates a significantly reduced crystallinity of the residue. In
1916
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds
4
4
Table 4 Atomic coordinates [· 10 ] and isotropic displacement par-
Table 5 Atomic coordinates [· 10 ] and isotropic displacement par-
˚
2
3
˚
2
3
ameters [A · 10 ] for [Mn(tren)(trenH)]SbS
4
(I). Estimated stand-
ameters [A · 10 ] for [Mn(chxn)
3 2 2 4 2 2
] [Mn(chxn) (SbS ) ]·6H O (II).
ard deviations are given in parenthesis.
Estimated standard deviations are given in parenthesis.
x
y
z
U
eq
x
y
z
U
eq
Mn
Sb
S(1)
S(2)
S(3)
S(4)
2879 (1)
6754 (1)
4710 (1)
5964 (1)
7886 (1)
8178 (1)
2442 (3)
1298 (3)
4605 (3)
1353 (3)
2114 (3)
2589 (3)
3883 (4)
3361 (6)
4460 (20)
1263 (5)
1218 (4)
3910 (11)
4590 (10)
3595 (11)
4914 (9)
2117 (4)
1005 (4)
1092 (4)
1257 (4)
1730 (4)
2991 (4)
2286 (4)
3196 (6)
6311 (1)
5125 (1)
6214 (1)
3100 (1)
6325 (1)
4894 (1)
8546 (3)
6489 (3)
7073 (3)
6687 (3)
1690 (2)
4171 (2)
3110 (3)
Ϫ1234 (4)
70 (20)
8767 (4)
7823 (4)
9121 (10)
8493 (10)
9199 (9)
8442 (9)
8940 (4)
8073 (4)
2243 (3)
3698 (3)
1872 (4)
1960 (4)
289 (3)
6230 (1)
7627 (1)
7785 (1)
7905 (1)
5689 (1)
9152 (1)
5186 (3)
4848 (2)
4723 (2)
7578 (2)
9397 (2)
6966 (2)
10275 (3)
9057 (4)
8920 (20)
4423 (4)
3886 (3)
4717 (8)
3961 (8)
4187 (9)
4515 (9)
6158 (4)
7090 (4)
8474 (4)
7742 (3)
10478 (3)
11099 (3)
9759 (3)
8836 (4)
29 (1)
32 (1)
37 (1)
48 (1)
51 (1)
44 (1)
44 (1)
42 (1)
43 (1)
42 (1)
41 (1)
36 (1)
44 (1)
85 (2)
93 (7)
63 (1)
55 (1)
48 (2)
53 (2)
55 (2)
52 (2)
58 (1)
60 (1)
55 (1)
50 (1)
53 (1)
54 (1)
56 (1)
80 (1)
Mn(1)
Mn(2)
Sb
S(1)
S(2)
7150 (1)
5000
5048 (1)
5000
3479 (1)
5000
39 (1)
49 (1)
35 (1)
43 (1)
45 (1)
57 (1)
60 (1)
47 (1)
45 (1)
46 (1)
45 (1)
41 (1)
44 (1)
66 (1)
70 (1)
60 (1)
63 (1)
63 (1)
107 (3)
99 (2)
58 (1)
56 (1)
57 (1)
65 (1)
81 (2)
92 (2)
60 (1)
53 (1)
52 (1)
53 (1)
83 (2)
86 (2)
55 (1)
64 (3)
94 (6)
72 (4)
79 (4)
122 (3)
146 (8)
155 (9)
182 (6)
126 (4)
76 (1)
77 (1)
90 (2)
132 (4)
6346 (1)
5917 (1)
7133 (1)
6124 (1)
6211 (1)
7189 (1)
6474 (1)
7538 (1)
7914 (1)
7020 (1)
6885 (1)
4994 (1)
5103 (1)
6465 (2)
6727 (2)
6722 (2)
6244 (3)
5978 (3)
5984 (2)
8022 (2)
8211 (2)
8718 (2)
9010 (2)
8836 (2)
8329 (2)
6749 (2)
6898 (2)
6629 (2)
6633 (2)
6486 (3)
6742 (2)
4937 (4)
5164 (6)
5246 (5)
4984 (6)
5157 (3)
5334 (9)
4990 (10)
5098 (4)
5053 (3)
8003 (2)
7741 (2)
5546 (3)
5437 (5)
4969 (1)
4842 (1)
4773 (1)
3739 (1)
6489 (1)
6408 (2)
5798 (2)
5684 (3)
4663 (3)
3598 (2)
4095 (2)
5883 (3)
6536 (3)
6783 (4)
6830 (4)
7845 (4)
8241 (5)
8190 (5)
7209 (3)
5338 (4)
5306 (4)
4977 (4)
5638 (5)
5634 (6)
5932 (4)
2953 (3)
3054 (3)
2392 (3)
1323 (4)
1228 (4)
1894 (3)
6948 (9)
6867 (12)
7178 (9)
7198 (10)
8282 (5)
8918 (18)
8924 (19)
8698 (7)
7593 (6)
2558 (3)
7854 (3)
5436 (7)
4908 (9)
5228 (1)
5892 (1)
6058 (1)
4325 (1)
4648 (1)
2849 (2)
3185 (2)
4657 (2)
3836 (2)
3888 (2)
2428 (2)
5936 (3)
4695 (3)
2872 (3)
2436 (3)
2127 (3)
1694 (5)
2098 (4)
2466 (3)
5025 (3)
4463 (3)
4839 (3)
5502 (4)
6057 (3)
5718 (3)
3254 (3)
2647 (3)
1974 (3)
2231 (4)
2814 (4)
3473 (3)
5711 (10)
5961 (10)
5335 (10)
5170 (10)
5110 (6)
5780 (15)
5556 (15)
6234 (9)
6411 (5)
4465 (3)
4177 (3)
7629 (6)
7904 (8)
S(3)
S(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(8Ј)
C(1)
C(2)
C(3)
C(4)
C(3Ј)
C(4Ј)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(19Ј)
C(20)
C(20Ј)
C(21)
C(22)
C(22Ј)
C(23)
C(24)
O(1)
62 (5)
equivalent isotropic Ueq calculated as one third of the trace of the orthogonalized Uij ten-
sor
addition, the CHNS content is only roughly in agreement
with the above discussed stepwise removal of the different
components of the compound. In summary, the thermal de-
composition of II is more complex involving redox reac-
tions between the constituents of the compound.
O(2)
O(3)
O(3Ј)
Experimental
[
Mn(tren)(trenH)]SbS
emental Mn (0.055 g; 1 mmol), Sb (0.121 g; 1 mmol) and S
0.128 g; 4 mmol) in 5 ml tren (Fluka; 99 %). The mixture was
4
: Yellow crystals were obtained reacting el-
Structure determination
(
heated to 140 °C for 7 days in a Teflon-lined steel autoclave (inner
volume ϳ30 ml) and was cooled to room temperature in the course
of 3 h. The crystalline yellow product (EDAX analysis (at%): Mn/
Sb/S: 1.05/1/3.94; CHNS-Analysis (%): C 24.37 (calc 24.09); H 6.23
Intensities were collected on STOE AED-II 4-circle-diffractometer
for I and on IPDS for II using monochromated MoK
α
radiation
˚
(
λ ϭ 0.71073 A). The intensities were corrected for Lorentz, pola-
rization and absorption effects. Structure solution was performed
(6.23); N 18.62 (18.72); S 21 (21.44)) was filtered off, washed with
2
using SHELXS-97 [21]. Refinement was done against F with
acetone and stored under vacuum. The compound is stable on air
for approximately one week and the yield based on Sb is about
SHELXL-97 [22]. All heavy atoms except C(22) and O(3) in II were
refined with anisotropic displacement parameters. In I the N(8)
atom of the monodentate tren ligand is partially disordered into
two positions and was refined using a split model with an occu-
pation ratio of 80:20 for N(8)/N(8Ј). The atoms C(3) and C(4) are
also disordered with final occupancies of 50:50 for the two split
positions. The hydrogen atoms except for that of N(7) were posi-
tioned with idealized geometry and refined with fixed isotropic dis-
placement parameters using a riding model. In II the atoms C(19),
C(20), C(22) and O(3) are disordered with final occupancies of
50:50 for the two split positions. All hydrogen atoms were posi-
tioned with idealised geometry. Technical details of data acqui-
sition and refinement results are summarised in Table 3. Tables 4
and 5 contain the atomic parameters of I and II.
80 %. The by-product was identified by X-ray powder diffraction
as elemental Sb.
[
Mn(chxn) [Mn(chxn)
3
]
2
2 4 2 2
(SbS ) ]·6H O: Bright yellow crystals were
synthesized from elemental Mn (0.82 g; 1.5 mmol), Sb (0.121 g;
1
1
1
mmol) and S (0.128 g; 4 mmol) in a solution of 5 ml 50 % trans-
,2-diaminocyclohexane (Merck; 99 %). The mixture was heated to
30 °C for 4 days in a Teflon-lined steel autoclave with an inner
volume of ϳ30 ml. After cooling to room temperature within 4 h
the crystalline product was filtered and washed with water and ace-
tone. The compound is stable on air and may also be obtained
under stirring conditions within 12 h. The yield of the stirred reac-
tion was 70 % based on Sb.
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918
zaac.wiley-vch.de
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1917

M. Schaefer, L. Engelke, W. Bensch
X-ray powder diffractometry: The X-ray powder patterns were re-
the single crystal data. We are also thankful to U. Cornelissen for
corded on a STOE Stadi-P diffractometer (Cu-Kα1 radiation, λ ϭ
carrying out the spectroscopic measurements.
˚
1.5406 A) in transmission geometry.
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[
2 3
formed using heating rates of 4 K min in Al O crucibles under
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[
[
[
[
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Scanning electron microscopy investigations and energy dispersive
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Crystallographic data (excluding structure factors) for the structure
reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication num-
bers CCDC 209261 for I and 209260 for II. Copies of the data can
be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1 EZ, UK [Fax: ϩ44-(0)1223-336033 or e-
mail: deposit@ccdc.cam.ac.uk].
5
[
2
[
[
[
21] G. M. Sheldrick, SHELXS 97, Program for the Solution of
Acknowledgements: Financial support by the Deutsche Forschungs-
gemeinschaft and the State of Schleswig-Holstein is gratefully
acknowledged. Our thanks are due to I. Jeß for the acquisition of
Crystal Structures, University of Göttingen, Germany 1997.
[22] G. M. Sheldrick, SHELXL 97, Program for the Refinement of
Crystal Structures, University of Göttingen, Germany 1997.
1918
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2003, 629, 1912Ϫ1918